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In the present work IR studies are discussed. The studies concerned TAED
(tetraacetyl ethylenediamine) bleach activator applied for peroxide-based
detergents. It was stated that infrared spectra of the coloured TAED
granules available in the washing powders are of the same nature as the
spectrum of commercial chemical reagent, and there is no influence of the
colourant applied. Depending on the temperature treatment an alkaline
TAED solutions can undergo transformation and degradation. Moreover,
the presence of hydrogen peroxide in the alkalined TAED solution
accelerates its transformation. There can be observed TAED-inorganic
support interaction, which nature depends on the pH of the solution.
1. INTRODUCTION
It has long been established that peroxygen bleaches that generate hydrogen
peroxide in the wash (such as perborate and percarbonate) are excellent stain
removal and textile whitening agents and that they are less aggressive to fabric
dyes than chlorine bleaches.
Dissolution of sodium perborate or sodium percarbonate under alkaline wash
conditions leads to the formation of the perhydroxyl ion (OOH-) [1]:
*
Author to whom all correspondence should be addressed.
TAED IR studies of bleach activator for peroxide-based detergents 219
moisture during storage of the detergent powder, the TAED should be suitably
protected by detergent compatible materials. For this reason producers supplies
TAED in granulated forms, e.g., product contains 92% (2%) active TAED
formulated as a coated/granulated product. The product has several colors
(mainly white, green, blue; Fig. 3) to choose depending on users choice
(Warwick International).
The chemical nature of the blue colorant is a copper phthalocyanine complex
CI (colour index) 74160 pigment blue 15 [9]. The green pigment is a similar
metal complex (polybromochloro copper phthalocyanine) CI 74265 pigment
green 36 [1].
According to the growing number of patents concerning its use in detergent
formulations, TAED will be found more often in detergents and therefore in the
natural media. In spite of its fairly low concentration in detergent formulations,
TAED and TAEDs by-products (e.g.: etylenediamine, acetic acid, TriAED -
triacetyl ethylenediamine) might have an impact on the environment. TAED is
very slightly lipophilic and TriAED (one of the most usual TAED by-product)
very hydrophilic. TriAED can therefore affect bacteria cells less than TAED.
TAED by-products could thus have less effect on aquatic life than TAED itself
[10].
a) b)
N
N
C C
C C Br5-6
C N N C
C N N C
N Cu N
N Cu N
C N N C
C N N C Cl 9-10
C C
C C N
N
Fig. 3. Structural formulae of the pigments which are present in the TAED granules:
a) pigment blue 15, b) pigment green 36 (Warwick International).
2. EXPERIMENTAL
421
440
1955
940
760
1845
60
584
552
Transmission (%)
618
1422
1025
1433
979
1325
40
1269
1357
1382
1681
1192
1707
20
a)
Transmission (a.u.)
b)
c)
Fig. 5. FT-IR spectra of TAED as: a) chemical reagent, and colored granules from
washing powders, blue and green (b and c, respectively).
224 J. Ryczkowski and S. Pasieczna
The permission level of the copper in the washing powder is less than 1 ppm [2],
so the existing amount of the colorants is probably below the detection limit of
the spectroscopy technique applied. This is the reason that recorded spectra are
in good agreement.
As it was pointed out in the experimental section, TAED is slightly soluble in
water and is going hydrolysis process (favored in acidic medium) to form
TriAED (equation (4)) and DAED (equation (5)) [5]:
Ac2N(CH2)2NAc2 + H2O AcNH(CH2)2NAc2 + AcOH (4)
AcNH(CH2)2NAc2 + H2O AcNH(CH2)2HNAc + AcOH (5)
Separate experiment with isolated DAED show that it is inert. The low
reactivity of DAED is typical of amides and due to resonance stabilization of the
amide bond [7]. However, it was confirmed, that TAED in the presence of
iron(III) undergoes further degradation and photodegradation [7].
Prior to the adsorption experiments an alkaline TAED solution was subjected
to temperature treatment. An appropriate amount of the solution was evaporated
and remaining solid residues were measured in a transmission mode (Fig. 6).
- 1237
a)
- 1239
- 1344
b)
- 1297
- 1341
- 1492
- 1645 -1637
Transmission (a.u.)
- 1345
c)
- 1414
- 1572
- 1415
- 1488 - 1489
- 1345
- 1451
d)
- 1415
- 1575
- 1450
- 1578
- 1493
- 1416
- 1448
- 1578
Fig. 6. Transformed TAED* from the alkaline solution evaporated at: a) 30oC, b) 50oC,
c) 80 oC, and d) 95oC.
TAED IR studies of bleach activator for peroxide-based detergents 225
V2O5 < SiO2 < TiO2 < ZrO2 < ZrO2-La < Al2O3 < La2O3 (6)
a)
- 1320
- 1238
- 1289
- 1367
- 1446
- 1238
Transmission (a.u.)
- 1561
- 1291
b)
- 1344
- 1653
- 1490
- 1648
- 1413
- 1574
Fig. 7. IR spectra of solid residues obtained after evaporation TAED solutions treated
with H2O2: a) neutral, b) alkalined.
- 1237
- 1289
- 1406
a)
- 1572
b)
Transmission (a.u.)
- 1638
- 1434
c)
- 1635
- 1574
- 1634
a)
b)
- 1410
- 1358
- 1568
Transmission (a.u.)
- 1352
- 1620
c)
- 1558
- 1412
d)
- 1637
- 1569
- 1634
- 1561
- 1462
a) OH2+ with C=O group (hydrogen bond for oxides characterized by low IEPS
value),
b) OH with the whole TAED* molecule (Van der Waals interaction for oxides
with the IEPS value around 7), and
c) O- with hydrogen (hydrogen bond for oxides characterized by IEPS value
8).
As far as the projection to environment is concerned, this work provides
information about the fate of TAED or more precisely its transformation by-
product TAED*. Adsorption phenomena, particular in an acidic aquatic
environments, can have an influence on the biodegradability of TAED*.
However, aquatic environments are open systems and other factors (e.g., the
presence of metal ions, photodegradation) can have a major impact on the
biodegradation process.
228 J. Ryczkowski and S. Pasieczna
4. CONCLUSIONS
In the present work there was shown mid IR spectrum of TAED. It was stated
that infrared spectra of the coloured TAED granules available in the washing
powders are of the same nature as the spectrum of commercial chemical reagent,
and there is no influence of the colourant. Depending on the temperature
treatment an alkaline TAED solutions undergo: transformation, partial
degradation, and deep degradation. An addition of hydrogen peroxide to the
neutral TAED aqueous solution causes its partial transformation. The presence
of H2O2 in the alkalined TAED solution accelerates the transformation to
TAED* (DAED). There can be observed TAED*-inorganic support interaction,
which is stronger in an acidic environment, weaker in an alkalic one, and very
weak in neutral.
REFERENCES
CURRICULA VITAE